EP0283712A1 - Process for removal of sulfur containing gases - Google Patents
Process for removal of sulfur containing gases Download PDFInfo
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- EP0283712A1 EP0283712A1 EP88102313A EP88102313A EP0283712A1 EP 0283712 A1 EP0283712 A1 EP 0283712A1 EP 88102313 A EP88102313 A EP 88102313A EP 88102313 A EP88102313 A EP 88102313A EP 0283712 A1 EP0283712 A1 EP 0283712A1
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- gases
- carried out
- carrier materials
- sulfur
- removal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
Definitions
- the present invention relates to a method for the selective removal of sulfur-containing gases from technical gases or exhaust gases by treatment with basic substances.
- DE-A 3 004 757 describes the removal of hydrogen sulfide from industrial gases by means of aqueous solutions of alkali metal hydroxides.
- carbon dioxide and hydrogen sulfide are removed from technical gas mixtures by means of washing with an aqueous solution of methyldiethanolamine.
- DE-A 3 027 220 also deals with the removal of hydrogen sulfide from industrial gases with aqueous alkali solutions.
- DE-A 3 427 133 and DE-A 3 427 134 and EP-A 173 908 processes for removing CO2 and / or H2S known, in which the removal is carried out in absorption liquids containing alkanolamine.
- DE-A 3 429 979 the removal of the acidic and / or sulfur-containing gases in aqueous solutions containing bases takes place in the presence of a basic ion exchanger having built-in tertiary or quaternary nitrogen atoms.
- the goal may be to remove only sulfur-containing gases from gas mixtures.
- the object of the present invention is to provide such a method.
- the present invention relates to a process for the selective removal of sulfur-containing gases from industrial gases or exhaust gases by treating the gases with basic substances, characterized in that the basic substances are carrier materials which are tertiary amino groups of the general formula have, where m and n each have values of 1 or 2 x and y each have values from 1 to 10, preferably 1 to 2 can accept, and R and R ⁇ are hydrogen or alkyl and R ⁇ are hydrogen or methyl.
- carrier materials are polymerization resins. These can be copolymers of polymerizable vinyl compounds which have the tertiary amino groups according to the invention either in the molecule itself or after appropriate functionalization.
- Polymerization resins crosslinked with polyvinyl compounds are particularly suitable.
- Examples of polyvinyl compounds are DVB, TVB, ethylene glycol dimethacrylate, methylene bisaryl amide, divinylethylene urea, octadiene 1.7, hexadiene 1.5 and Triallyl cyanurate for use.
- the functionalization to the claimed resins takes place according to methods known per se.
- Ion exchangers and their precursors of the type mentioned are known. You and their manufacture will, for. B. described in F. Helfferich, ion exchanger, Volume 1, 1959, pages 10 to 106 and Ullmann's encyclopedia of techn. Chemie, 4th edition, volume 13, 1977, pages 292 to 309.
- polyamines such as. B. triethylenetetramine or suitable hydrazine derivatives can be used.
- Further preferred carrier materials are condensation resins which have the tertiary amino groups according to the invention.
- Such resins are known. They are obtained, for example, by reacting aliphatic and / or aromatic amines with epichlorohydrin or formaldehyde.
- aliphatic amines are polyalkylene polyamines, such as diethylenetriamine, triethylene tetramine, and aromatic amines, for example m-phenylenediamine.
- the ethanolamine or propanolamine groups according to the invention can advantageously be obtained by reacting the corresponding resins with ethylene oxide or propylene oxide.
- the method according to the invention is suitable for the removal of sulfur-containing gases.
- sulfur-containing gases are in particular hydrogen sulfide, carbon disulfide, carbon oxysulfide and sulfur dioxide.
- the sulfur-containing gas is SO2.
- the sulfur-containing gases can be selectively separated from other gases. It is possible to remove sulfur-containing gases from gases with a high CO2 content.
- Applications are in the desulfurization of domestic fire, in the removal of SO2 in the Clauss process, in the exhaust gas desulfurization of power plants, sulfuric acid plants, refineries and calcining processes.
- the gases or exhaust gases to be treated are brought into contact with the carrier materials according to the invention. Since the gases to be cleaned generally contain sufficient moisture, the support materials according to the invention can be used as such without further pretreatment with their respective water content, ie not in an aqueous environment as in the known processes. In the case of gases which are too dry, it is sufficient to use known processes to moisten or spray the contact layer itself with water.
- the amount of carrier materials used depends on the concentration of the sulfur-containing gases in the technical gases to be treated.
- the amount of carrier materials is 5 to 500 l, preferably 10 to 50 l, per Nm3 / h of gas to be treated. In principle, higher or lower amounts of the carrier materials can also be used.
- the sulfur-containing gases are preferably removed at room temperature (approx. 10 to 30 ° C.). It takes two to seven days to fully saturate the resin under the conditions described.
- a particularly preferred embodiment of the method according to the invention consists in that the carrier materials are regenerated after their saturation.
- the HCl used here preferably has a concentration of 3 to 10%, but even when 36% HCl is used, there is generally no damage to the carrier materials.
- the reactivation is carried out with sodium hydroxide solution at a concentration of 3 to 50%, preferably 5 to 10%.
- regeneration is carried out at elevated temperature using sodium hydroxide solution or water vapor. No additional chlorides are generated here.
- the regeneration with sodium hydroxide solution is carried out at temperatures between 120 and 200 ° C., preferably 130 to 160 ° C.
- the sodium hydroxide solution preferably has a concentration in the range from 5 to 30%.
- temperatures between 180 and 235 ° C are preferred.
- the pressure of the water vapor is between 9 and 30 bar.
- the gas (5) to be cleaned is passed through one of two absorption towers (7) filled with carrier materials and leaves it as cleaned gas (6).
- Sodium hydroxide solution (1) and water (2) are mixed in the replenisher (3).
- the regenerant stream (4) is passed through the absorption tower (7) in which the carrier materials are already saturated.
- the used regeneration agent (8) is removed from the system and can then be processed.
- the purified gas removed from the system via line (6) has a greatly reduced content of sulfur-containing impurities compared to the unpurified gas. For example, it is possible to reduce the sulfur content of CO2 / SO2 gas mixtures with an SO2 concentration between 2,500 and 13,500 ppm almost quantitatively (> 98%).
- a styrene / divinylbenzene copolymer resin which is equipped with aminobenzyl groups was reacted with 2.2 mol of ethylene oxide.
- the reaction was carried out at 80 ° C. in an aqueous medium, without a catalyst and using a 10% excess of ethylene oxide. According to IR spectra, it was quantitative.
- the finished resin In contrast to the preliminary product (amine smell), the finished resin was characterized by absolute odorlessness. While the preliminary product became much darker at temperatures of approx. 120 ° C, the final product retained its originally light color. Both properties are the result of the good chemical resistance of the functional N, N-bis ( ⁇ -hydroxyethyl) benzylamino group.
- Example 1 100 ml of the moist resin prepared according to Example 1 were placed in a stainless steel tube designed as a reactor.
- the gas mixture CO2 / SO2 was produced in a 60 l pressure bottle, a concentration of 1000 -1500 ppm being set.
- the analytical control was carried out by iodometric titration using a Mettler memotitrator.
- the resin from the pressure bottle was pressurized at 40 l / hour via rotameter.
- the gas emerging from the reactor was passed through an iodine / potassium iodide solution, the content of which was checked at regular intervals by titration.
- the result of the test is shown graphically in FIG. 2.
- the relative SO2 adsorption of the resin was based on a volume of 1000 ml and applied against the amount of SO2 (mol) contained in the applied gas mixture.
- the curve shows that practically quantitative SO2 adsorption takes place, and the breakthrough of SO2 begins at 1.85 mol.
- the rapid drop from almost 100% at 1.85 mol to zero at 2.4 mol illustrates the high efficiency of the resin.
- the resin saturated with SO2 can be regenerated excellently with 5 bed volumes of 4% sodium hydroxide solution at room temperature.
- the resin regenerated in this way showed the same adsorption properties as the freshly produced resin when loaded again.
- Example 2 In the test arrangement described in Example 2, the gas mixtures listed in Table 1 were passed through 500 ml of the resin prepared according to Example 1.
Abstract
Die vorliegende Erfindung betrifft ein Verfahren zur selektiven Entfernung schwefelhaltiger Gase asu technischen Gasen oder Abgasen durch Behandlung mit basischen Substanzen.The present invention relates to a method for the selective removal of sulfur-containing gases and industrial gases or exhaust gases by treatment with basic substances.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur selektiven Entfernung schwefelhaltiger Gase aus technschen Gasen oder Abgasen durch Behandlung mit basischen Substanzen.The present invention relates to a method for the selective removal of sulfur-containing gases from technical gases or exhaust gases by treatment with basic substances.
Verfahren zur Entfernung von schwefelhaltigen Gasen aus technischen Gasen oder Abgasen sind bereits bekannt. So beschreibt die DE-A 3 004 757 die Entfernung von Schwefelwasserstoff aus technischen Gasen mittels wäßriger Lösungen von Alkalimetallhydroxiden. Gemäß den DE-A 3 236 600 und De-A 3 236 601 erfolgt die Entfernung von Kohlendioxid und Schwefelwasserstoff aus technischen Gasmischungen mittels einer Wäsche mit einer wäßrigen Lösung von Methyldiethanolamin. Auch die DE-A 3 027 220 befaßt sich mit der Entfernung von Schwefelwasserstoff aus technischen Gasen mit wäßrigen Alkalilösungen.Methods for removing sulfur-containing gases from industrial gases or exhaust gases are already known. DE-A 3 004 757 describes the removal of hydrogen sulfide from industrial gases by means of aqueous solutions of alkali metal hydroxides. According to DE-A 3 236 600 and De-A 3 236 601, carbon dioxide and hydrogen sulfide are removed from technical gas mixtures by means of washing with an aqueous solution of methyldiethanolamine. DE-A 3 027 220 also deals with the removal of hydrogen sulfide from industrial gases with aqueous alkali solutions.
Ferner sind aus den DE-A 3 427 133 und DE-A 3 427 134 sowie der EP-A 173 908 Verfahren zum Entfernen von CO₂ und/oder H₂S bekannt, in denen die Entfernung in Alkanolamin enthaltenden Absorptionsflüssigkeiten durchgeführt wird. Gemäß der DE-A 3 429 979 geschieht die Entfernung der sauren und/oder schwefelhaltigen Gase in Basen enthaltenden wäßrigen Lösungen in Gegenwart eines, eingebaute tertiäre oder quarternäre Stickstoffatome aufweisenden basischen Ionenaustauschers.Furthermore, from DE-A 3 427 133 and DE-A 3 427 134 and EP-A 173 908 processes for removing CO₂ and / or H₂S known, in which the removal is carried out in absorption liquids containing alkanolamine. According to DE-A 3 429 979, the removal of the acidic and / or sulfur-containing gases in aqueous solutions containing bases takes place in the presence of a basic ion exchanger having built-in tertiary or quaternary nitrogen atoms.
Unter besonderen Gegebenheiten kann es das Ziel sein, ausschließlich schwefelhaltige Gase aus Gasgemischen zu entfernen. Die Aufgabe des vorliegenden Erfindung ist die Bereitstellung eines solchen Verfahrens.Under certain circumstances, the goal may be to remove only sulfur-containing gases from gas mixtures. The object of the present invention is to provide such a method.
Es wurde nunmehr ein Verfahren zur selektiven Entfernung von schwefelhaltigen Gasen gefunden, welches in überraschend einfacher Weise durchführbar ist und darüber hinaus sehr gute Resultate bringt. Bei diesem Verfahren werden als basische Substanzen Tertiäre Amingruppen enthaltende Trägermaterialien eingesetzt.A method has now been found for the selective removal of sulfur-containing gases, which can be carried out in a surprisingly simple manner and, moreover, brings very good results. In this process, carrier materials containing tertiary amine groups are used as basic substances.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur selektiven Entfernung schwefelhaltiger Gase aus technischen Gasen oder Abgasen durch Behandlung der Gase mit basischen Substanzen, dadurch gekennzeichnet, daß die basischen Substanzen Trägermaterialien sind, die tertiäre Aminogruppen der allgemeinen Formel
m und n jeweils Werte von 1 oder 2
x und y jeweils Werte von 1 bis 10, bevorzugt 1 bis 2
annehmen können, und
R und Rʹ Wasserstoff oder Alkyl und
Rʺ Wasserstoff oder Methyl sind.The present invention relates to a process for the selective removal of sulfur-containing gases from industrial gases or exhaust gases by treating the gases with basic substances, characterized in that the basic substances are carrier materials which are tertiary amino groups of the general formula
m and n each have values of 1 or 2
x and y each have values from 1 to 10, preferably 1 to 2
can accept, and
R and Rʹ are hydrogen or alkyl and
Rʺ are hydrogen or methyl.
Als Trägermaterialien im Sinne dieser Erfindung sind sowohl anorganische als auch organische Substanzen geeignet. Eine bevorzugte Verfahrensvariante des erfindungsgemäßen Verfahrens besteht darin, daß die Trägermaterialien Polymerisationsharze sind. Dies können Copolymere aus polymerisierbaren Vinylverbindungen sein, die entweder im Molekül selbst oder nach entsprechender Funktionalisierung die erfindungsgemäßen tertiären Aminogruppen aufweisen.Both inorganic and organic substances are suitable as carrier materials in the sense of this invention. A preferred process variant of the process according to the invention is that the carrier materials are polymerization resins. These can be copolymers of polymerizable vinyl compounds which have the tertiary amino groups according to the invention either in the molecule itself or after appropriate functionalization.
Mit Polyvinylverbindungen vernetzte Polymerisationsharze sind besonders geeignet. Als Monovinylverbindungen sollen stellvertretend Styrol, Chlorstyrole, Alkylstyrole, Chlormethylstyrole, (Meth)acrylate (C₁ - C₆), (Meth)acrylamide bzw. (Meth)acrylamide auf Basis Polyamin, Glycidylmethacrylat und Vinylglycidylether genannt sein. Als Polyvinylverbindungen kommen beispielsweise DVB, TVB, Ethylenglykoldimethacrylat, Methylenbiscarylamid, Divinylethylenharnstoff, Octadien 1,7, Hexadien 1,5 und Triallylcyanurat zum Einsatz. Die Funktionalisierung zu den beanspruchten Harzen erfolgt nach an sich bekannten Verfahren.Polymerization resins crosslinked with polyvinyl compounds are particularly suitable. Representative styrene, chlorostyrenes, alkylstyrenes, chloromethylstyrenes, (meth) acrylates (C₁ - C₆), (meth) acrylamides or (meth) acrylamides based on polyamine, glycidyl methacrylate and vinyl glycidyl ether should be mentioned as monovinyl compounds. Examples of polyvinyl compounds are DVB, TVB, ethylene glycol dimethacrylate, methylene bisaryl amide, divinylethylene urea, octadiene 1.7, hexadiene 1.5 and Triallyl cyanurate for use. The functionalization to the claimed resins takes place according to methods known per se.
Ionenaustauscher bzw. deren Vorprodukte der genannten Art sind bekannt. Sie und ihre Herstellung werden z. B. beschrieben in F. Helfferich, Ionenaustauscher, Band 1, 1959, Seiten 10 bis 106 und Ullmanns Enzyklopädie der techn. Chemie, 4. Aufl., Band 13, 1977, Seiten 292 bis 309. Zur Funktionalisierung können auch Polyamine wie z. B. Triethylentetramin oder geeignete Hydrazin-Abkömmlinge eingesetzt werden.Ion exchangers and their precursors of the type mentioned are known. You and their manufacture will, for. B. described in F. Helfferich, ion exchanger,
Weitere bevorzugte Trägermaterialien stellen Kondensationsharze dar, die die erfindungsgemäßen tertiären Aminogruppen aufweisen.Further preferred carrier materials are condensation resins which have the tertiary amino groups according to the invention.
Die Herstellung derartiger Harze ist bekannt. Man erhält sie beispielsweise durch Umsetzung von aliphatischen und/oder aromatischen Aminen mit Epichlorhydrin bzw. Formaldehyd. Als aliphatische Amine seien beispielsweise Polyalkylenpolyamine genannt, wie Diethylentriamin, Triethylentetramin, als aromatisches Amin beispielsweise m-Phenylendiamin.The production of such resins is known. They are obtained, for example, by reacting aliphatic and / or aromatic amines with epichlorohydrin or formaldehyde. Examples of aliphatic amines are polyalkylene polyamines, such as diethylenetriamine, triethylene tetramine, and aromatic amines, for example m-phenylenediamine.
Die erfindungsgemäßen Ethanolamin- bzw. Propanolamingruppen können vorteilhaft durch Umsetzung der entsprechenden Harze mit Ethylenoxid bzw. Propylenoxid erhalten werden.The ethanolamine or propanolamine groups according to the invention can advantageously be obtained by reacting the corresponding resins with ethylene oxide or propylene oxide.
Das erfindungsgemäße Verfahren eignet sich für die Entfernung von schwefelhaltigen Gasen. Dies sind im Rahmen dieser Erfindung insbesondere Schwefelwasserstoff, Schwefelkohlenstoff, Kohlenoxisulfid und Schwefeldioxid.The method according to the invention is suitable for the removal of sulfur-containing gases. In the context of this invention, these are in particular hydrogen sulfide, carbon disulfide, carbon oxysulfide and sulfur dioxide.
Gemäß einer besonders bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens ist das schwefelhaltige Gas SO₂. Durch die Anwendung des erfindungsgemäßen Verfahrens können die schwefelhaltigen Gase selektiv von anderen Gasen getrennt werden. So ist es möglich, schwefelhaltige Gase aus Gasen mit hohem CO₂-Gehalt zu entfernen.According to a particularly preferred embodiment of the process according to the invention, the sulfur-containing gas is SO₂. By using the method according to the invention, the sulfur-containing gases can be selectively separated from other gases. It is possible to remove sulfur-containing gases from gases with a high CO₂ content.
Anwendungsfälle liegen bei der Entschwefelung von Hausbrand, bei der Entfernung von SO₂ bei dem Clauß-Prozeß, bei der Abgasentschwefelung von Kraftwerken, Schwefelsäureanlagen, Raffinerien und Kalzinierprozessen.Applications are in the desulfurization of domestic fire, in the removal of SO₂ in the Clauss process, in the exhaust gas desulfurization of power plants, sulfuric acid plants, refineries and calcining processes.
Beim erfindungsgemäßen Verfahren werden die zu behandelnden Gase bzw. Abgase mit den erfindungsgemäßen Trägermaterialien in Kontakt gebracht. Da die zu reinigenden Gase im allgemeinen genügend Feuchte enthalten, können die erfindungsgemäßen Trägermaterialien als solche ohne weitere Vorbehandlung mit ihrem jeweiligen Wassergehalt eingesetzt werden, d. h. nicht in einer wäßrigen Umgebung wie bei den bekannten Verfahren Im Falle zu trockener Gase genügt es, diese nach bekannten Verfahren zu befeuchten oder auch die Kontaktschicht selbst mit Wasser zu besprühen.In the method according to the invention, the gases or exhaust gases to be treated are brought into contact with the carrier materials according to the invention. Since the gases to be cleaned generally contain sufficient moisture, the support materials according to the invention can be used as such without further pretreatment with their respective water content, ie not in an aqueous environment as in the known processes. In the case of gases which are too dry, it is sufficient to use known processes to moisten or spray the contact layer itself with water.
Die Menge der zum Einsatz Trägermaterialien richtet sich nach der Konzentration der schwefelhaltigen Gase in den zu behandelnden technischen Gasen. Die Menge der Trägermaterialien beträgt 5 bis 500 ℓ, bevorzugt 10 bis 50 ℓ, pro Nm³/h zu behandelndes Gas. Auch höhere oder niedrigere Mengen der Trägermaterialien können im Prinzip eingesetzt werden.The amount of carrier materials used depends on the concentration of the sulfur-containing gases in the technical gases to be treated. The amount of carrier materials is 5 to 500 ℓ, preferably 10 to 50 ℓ, per Nm³ / h of gas to be treated. In principle, higher or lower amounts of the carrier materials can also be used.
Die Entfernung der schwefelhaltigen Gase wird bevorzugt bei Raumtemperatur (ca. 10 bis 30°C) vorgenommen. Bis zur vollständigen Sättigung des Harzes dauert es unter den beschriebenen Bedingungen zwei bis sieben Tage. Eine besonders bevorzugte Ausführungsform des erfindungsgemäßen Verfahrens besteht darin, daß die Trägermaterialien nach ihrer Sättigung regeneriert werden.The sulfur-containing gases are preferably removed at room temperature (approx. 10 to 30 ° C.). It takes two to seven days to fully saturate the resin under the conditions described. A particularly preferred embodiment of the method according to the invention consists in that the carrier materials are regenerated after their saturation.
Je nach den entsprechenden Gegebenheiten ist die Durchführung der Regenerierung vorteilhaft nach den drei im folgenden erläuterten Verfahren durchführbar. Eine bevorzugtes Verfahren ist dadurch gekennzeichnet, daß die Regenerierung bei Raumtemperatur durch
- a) Behandlung der Trägermaterialien mit HCl und anschließende Entfernung der nicht verbrauchten HCl durch Waschen mit Wasser
- b) sowie die Aktivierung mit Natronlauge vorgenommen wird, wobei die überschüssige Natronlauge anschließend mit Wasser entfernt wird.
- a) Treatment of the carrier materials with HCl and subsequent removal of the unused HCl by washing with water
- b) and the activation is carried out with sodium hydroxide solution, the excess sodium hydroxide solution then being removed with water.
Die dabei eingesetzte HCl hat bevorzugt eine Konzentration von 3 bis 10 %, aber auch beim Einsatz von 36 %iger HCl treten im allgemeinen keine Schädigungen an den Trägermaterialien auf. Die Reaktivierung wird mit Natronlauge einer Konzentration von 3 bis 50 %, bevorzugt 5 bis 10 %, vorgenommen.The HCl used here preferably has a concentration of 3 to 10%, but even when 36% HCl is used, there is generally no damage to the carrier materials. The reactivation is carried out with sodium hydroxide solution at a concentration of 3 to 50%, preferably 5 to 10%.
In den beiden alternativen, im folgenden beschriebenen Verfahren geschieht die Regenerierung bei erhöhter Temperatur mit Natronlauge oder Wasserdampf. Es werden hierbei also keine zusätzlichen Chloride erzeugt. Die Regenerierung mit Natronlauge wird dabei bei Temperaturen zwischen 120 und 200°C, bevorzugt 130 bis 160°C, vorgenommen. Die Natronlauge weist bevorzugt eine Konzentration im Bereich von 5 bis 30 % auf.In the two alternative processes described below, regeneration is carried out at elevated temperature using sodium hydroxide solution or water vapor. No additional chlorides are generated here. The regeneration with sodium hydroxide solution is carried out at temperatures between 120 and 200 ° C., preferably 130 to 160 ° C. The sodium hydroxide solution preferably has a concentration in the range from 5 to 30%.
Wird die Regenerierung mit Wasserdampf vorgenommen, sind Temperaturen zwischen 180 und 235°C bevorzugt. Der Druck des Wasserdampfes liegt zwischen 9 und 30 bar.If the regeneration is carried out with steam, temperatures between 180 and 235 ° C are preferred. The pressure of the water vapor is between 9 and 30 bar.
In Fig. 1 ist eine Möglichkeit zur Durchführung des erfindungsgemäßen Verfahrens dargestellt. In dieser Zeichnung bedeuten:
- (1) NaOH
- (2) H₂O
- (3) Regeneriermittelvorlage
- (4) Regeneriermittelstrom
- (5) zu reinigendes Gas
- (6) gereinigtes Gas
- (7) Absorptionstürme
- (8) verbrauchtes Regeneriermittel
- (1) NaOH
- (2) H₂O
- (3) Regenerant template
- (4) regenerant flow
- (5) gas to be cleaned
- (6) purified gas
- (7) absorption towers
- (8) used regenerant
Das zu reinigende Gas (5) wird durch jeweils einen von zwei mit Trägermaterialien gefüllten Absorptionstürmen (7) geleitet und verläßt diesen als gereinigtes Gas (6). Natronlauge (1) und Wasser (2) werden in der Regeneriermittelvorlage (3) gemischt. Der Regeneriermittelstrom (4) wird jeweils durch den Absorptionsturm (7) geleitet, in dem die Trägermaterialien bereits gesättigt sind. Das verbrauchte Regeneriermittel (8) wird dem System entnommen und kann dann aufbereitet werden.The gas (5) to be cleaned is passed through one of two absorption towers (7) filled with carrier materials and leaves it as cleaned gas (6). Sodium hydroxide solution (1) and water (2) are mixed in the replenisher (3). The regenerant stream (4) is passed through the absorption tower (7) in which the carrier materials are already saturated. The used regeneration agent (8) is removed from the system and can then be processed.
Das über die Leitung (6) dem System entnommene gereinigte Gas weist einen im Vergleich zum ungereinigten Gas stark verminderten Gehalt an schwefelhaltigen Verunreinigungen auf. So ist es beispielsweise möglich, den Schwefelgehalt von CO₂/SO₂-Gasgemischen mit einer SO₂-Konzentration zwischen 2.500 und 13.500 ppm fast quantitativ (> 98 %) zu senken.The purified gas removed from the system via line (6) has a greatly reduced content of sulfur-containing impurities compared to the unpurified gas. For example, it is possible to reduce the sulfur content of CO₂ / SO₂ gas mixtures with an SO₂ concentration between 2,500 and 13,500 ppm almost quantitatively (> 98%).
Die Durchführung des erfindungsgemäßen Verfahrens ist selbstverständlich nicht auf die zwingende Verwendung der lediglich beispielhaften Vorrichtung gemäß Zeichnung angewiesen.The implementation of the method according to the invention is of course not dependent on the mandatory use of the merely exemplary device according to the drawing.
Die nachfolgenden Beispiele dienen der weiteren Erläuterung des erfindungsgemäßen Verfahrens, ohne dieses zu beschränken.The following examples serve to further explain the process according to the invention without restricting it.
Ein Styrol/Divinylbenzol-Copolymerharz, welches mit Aminobenzylgruppen ausgerüstet ist, (Typ MP 64 ZII) wurde mit 2,2 Mol Ethylenoxid umgesetzt.
Die Umsetzung erfolgte bei 80°C im wäßrigen Medium, ohne Katalysator und unter Einsatz eines 10%igen Ethylenoxid-Überschusses. Sie verlief - laut IR-Spektren - quantitativ.The reaction was carried out at 80 ° C. in an aqueous medium, without a catalyst and using a 10% excess of ethylene oxide. According to IR spectra, it was quantitative.
Das fertige Harz zeichnete sich, im Gegensatz zum Vorprodukt (Amingeruch) durch absolute Geruchlosigkeit aus. Während das Vorprodukt bei Temperaturen von ca. 120°C deutlich dunkler wurde, bewahrte das Endprodukt seine ursprünglich helle Farbe. Beide Eigenschaften sind das Resultat der guten chemischen Beständigkeit der funktionellen N,N-bis-(β-hydroxyethyl)-benzylamino-Gruppe.In contrast to the preliminary product (amine smell), the finished resin was characterized by absolute odorlessness. While the preliminary product became much darker at temperatures of approx. 120 ° C, the final product retained its originally light color. Both properties are the result of the good chemical resistance of the functional N, N-bis (β-hydroxyethyl) benzylamino group.
Es wurden 100 ml des nach Beispiel 1 hergestellten feuchten Harzes in ein als Reaktor ausgelegtes Edelstahlrohr gefüllt. Die Gasmischung CO₂/SO₂ wurde in einer 60 l Druckflasche hergestellt, wobei eine Konzentration von 1000 -1500 ppm eingestellt wurde. Die analytische Kontrolle erfolgte durch iodometrische Titration mittels Mettler-Memotitrator. Die Beaufschlagung des Harzes aus der Druckflasche mit 40 l/Stunde erfolgte über Rotameter.100 ml of the moist resin prepared according to Example 1 were placed in a stainless steel tube designed as a reactor. The gas mixture CO₂ / SO₂ was produced in a 60 l pressure bottle, a concentration of 1000 -1500 ppm being set. The analytical control was carried out by iodometric titration using a Mettler memotitrator. The resin from the pressure bottle was pressurized at 40 l / hour via rotameter.
Zwecks Kontrolle der Wirksamkeit des Harzes wurde das aus dem Reaktor austretende Gas durch eine Jod/Kaliumjodid-Lösung geleitet, die in gewissen Zeitabständen durch Titration auf ihren Gehalt überprüft wurde.In order to check the effectiveness of the resin, the gas emerging from the reactor was passed through an iodine / potassium iodide solution, the content of which was checked at regular intervals by titration.
Das Resultat des Versuches ist in der Figur 2 graphisch dargestellt. Dabei wurde die relative SO₂-Adsorption des Harzes auf ein Volumen von 1000 ml bezogen und gegen die in der beaufschlagten Gasmischung enthaltenen SO₂-Menge (Mol) aufgetragen.The result of the test is shown graphically in FIG. 2. The relative SO₂ adsorption of the resin was based on a volume of 1000 ml and applied against the amount of SO₂ (mol) contained in the applied gas mixture.
Die Kurve zeigt, daß zunächst praktisch eine quantitative SO₂-Adsorption erfolgt, und bei 1,85 Mol der Durchschlag des SO₂ beginnt. Der rasche Abfall von nahezu 100% bei 1,85 Mol auf Null bei 2,4 Mol verdeutlicht den hohen Wirkungsgrad des Harzes.The curve shows that practically quantitative SO₂ adsorption takes place, and the breakthrough of SO₂ begins at 1.85 mol. The rapid drop from almost 100% at 1.85 mol to zero at 2.4 mol illustrates the high efficiency of the resin.
Damit absorbierte das Harz bis zum Durchburch, 118,4 g SO₂, entsprechend ca. 17% seines Eigengewichtes (1 Liter = 0,7 kg).The resin absorbed until breakthrough, 118.4 g SO₂, corresponding to approx. 17% of its own weight (1 liter = 0.7 kg).
Das mit SO₂ gesättigte Harz läßt sich hervorragend mit 5 Bettvolumen 4 %iger Natronlauge bei Raumtemperatur regenerieren.The resin saturated with SO₂ can be regenerated excellently with 5 bed volumes of 4% sodium hydroxide solution at room temperature.
Das auf diesem Wege regenerierte Harz zeigte bei erneuter Beladung die gleichen Adsorptionseigenschaften wie das frisch hergestellte Harz.The resin regenerated in this way showed the same adsorption properties as the freshly produced resin when loaded again.
In der in Beispiel 2 beschriebenen Versuchsanordnung wurden durch 500 ml des nach Beispiel 1 hergestellten harzes die in Tabelle 1 aufgeführten Gasmischungen geleitet.
Innerhalb der letzten 2 Stunden der Beaufschlagung ging die Adsorption von über 98 % des angebotenen SO₂ auf 0 % zurück. Damit wurden bei dieser Versuchsdurchführung ca. 1,50 Mol SO₂ pro Liter Harz adsorbiert. Die Regenerierung erfolgt mit 5 Bettvolumen 4 %iger NaOH.Within the last 2 hours of exposure, the adsorption decreased from over 98% of the SO₂ offered to 0%. In this way, approximately 1.50 moles of SO₂ per liter of resin were adsorbed in this test procedure. Regeneration is carried out with 5 bed volumes of 4% NaOH.
Claims (10)
m und n jeweils Werte von 1 oder 2
x und y jeweils Werte von 0 bis 10, bevorzugt 0 bis 2
annehmen können, und
R und Rʹ Wasserstoff oder Alkyl und
Rʺ Wasserstoff oder Methyl sind.1. A process for the selective removal of sulfur-containing gases from industrial gases or exhaust gases by treating the gases with basic substances, characterized in that the basic substances are carrier materials, the tertiary amino groups of the general formula
m and n each have values of 1 or 2
x and y each have values from 0 to 10, preferably 0 to 2
can accept, and
R and Rʹ are hydrogen or alkyl and
Rʺ are hydrogen or methyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873706619 DE3706619A1 (en) | 1987-03-01 | 1987-03-01 | METHOD FOR REMOVING SULFURIZING GASES |
| DE3706619 | 1987-03-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0283712A1 true EP0283712A1 (en) | 1988-09-28 |
Family
ID=6322071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88102313A Withdrawn EP0283712A1 (en) | 1987-03-01 | 1988-02-18 | Process for removal of sulfur containing gases |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4853191A (en) |
| EP (1) | EP0283712A1 (en) |
| JP (1) | JPH01288319A (en) |
| BR (1) | BR8800868A (en) |
| DE (1) | DE3706619A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248321A (en) * | 1992-08-06 | 1993-09-28 | The Research Foundation Of State University Of New York At Buffalo | Process of removing sulfur oxides from gaseous mixtures |
| US6576044B1 (en) | 1999-02-25 | 2003-06-10 | The Boc Group, Inc. | Process for the purification of nitric oxide |
| US7302043B2 (en) * | 2004-07-27 | 2007-11-27 | Gatan, Inc. | Rotating shutter for laser-produced plasma debris mitigation |
| JP6615813B2 (en) | 2017-03-23 | 2019-12-04 | 株式会社東芝 | Carbon dioxide absorbent and carbon dioxide separation and recovery system |
| CN109200734B (en) * | 2017-06-30 | 2021-06-04 | 中国石油化工股份有限公司 | Method for treating oxidized tail gas in hydrogen peroxide production process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2962344A (en) * | 1959-01-13 | 1960-11-29 | Kurmeier Hans Heinrich | Deodorizing of gases |
| DE2453549A1 (en) * | 1973-12-31 | 1975-07-31 | Heinrich Dr Phil Riemer | Removal of odorants from gases - by passing through mixts. of porous non-ionic resin and basic ion-exchange resin |
| DE2533103A1 (en) * | 1974-07-24 | 1976-02-05 | Union Carbide Corp | METHOD OF REMOVING SO DEEP 2 FROM GAS MIXTURES |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196175A (en) * | 1977-01-03 | 1980-04-01 | Chevron Research Company | Process for removing a bisulfite salt from an aqueous solution by chemisorption |
| US4283373A (en) * | 1980-03-17 | 1981-08-11 | The Goodyear Tire & Rubber Company | Method for removal of sulfur compounds from a gas |
| DE3236600A1 (en) * | 1982-10-02 | 1984-04-05 | Basf Ag, 6700 Ludwigshafen | METHOD FOR REMOVING CO (DOWN ARROW) 2 (DOWN ARROW) AND, IF NECESSARY, H (DOWN ARROW) 2 (DOWN ARROW) S FROM NATURAL GAS |
| US4737166A (en) * | 1986-12-30 | 1988-04-12 | Bend Research, Inc. | Acid gas scrubbing by composite solvent-swollen membranes |
-
1987
- 1987-03-01 DE DE19873706619 patent/DE3706619A1/en not_active Withdrawn
-
1988
- 1988-02-18 EP EP88102313A patent/EP0283712A1/en not_active Withdrawn
- 1988-02-23 JP JP63038775A patent/JPH01288319A/en active Pending
- 1988-02-25 US US07/159,147 patent/US4853191A/en not_active Expired - Fee Related
- 1988-02-29 BR BR8800868A patent/BR8800868A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2962344A (en) * | 1959-01-13 | 1960-11-29 | Kurmeier Hans Heinrich | Deodorizing of gases |
| DE2453549A1 (en) * | 1973-12-31 | 1975-07-31 | Heinrich Dr Phil Riemer | Removal of odorants from gases - by passing through mixts. of porous non-ionic resin and basic ion-exchange resin |
| DE2533103A1 (en) * | 1974-07-24 | 1976-02-05 | Union Carbide Corp | METHOD OF REMOVING SO DEEP 2 FROM GAS MIXTURES |
Non-Patent Citations (1)
| Title |
|---|
| INDUSTRIAL ENGINEERING CHEMISTRY PROD. RES. DEVELOP., Band 12, Nr. 4, 1973, Seiten 288-293; A.S. VAIDYANATHAN et al.: "Sorption of sulfur dioxide, hydrogen sulfide, and nitrogen dioxide by ion-exchange resins" * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3706619A1 (en) | 1988-09-22 |
| US4853191A (en) | 1989-08-01 |
| BR8800868A (en) | 1988-10-11 |
| JPH01288319A (en) | 1989-11-20 |
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